Process of limiting polymerization



Patented Oct. 7, 1952 Yamazso PROGESS IJJMH rotrmshizarios N Drawing- Application Jinn/1a 194a; 1 C

claims.- (or. regna- The present invention is a continuation-inpart of my Patent No. 2,440,909 issued May 4, 4 on appl ca Se ial.N .,560,900,n1ed O tober 28, 1944, and my co-pendin'g application No. 7 .1 fi ed Oct er v.15 194 .7; ab d ned, and several articles in the Journal of the American Chemical Society, vol. 63,;p. 1731 (1941) volf 65, p.629 (1943) and vol. 67, p.-:1l76 (1945). l

Generally, the above citedreferencedas well as the present invention deal with limiting and,

controlling direct. and indirectrphenolealdehyde condensations by means of blocked phenols.

In the above cited pat ent, patent application and publications the amount or blocked/f or in only one ring position reactive, phenol used, was never less than equimolar quantities, or even double molar quantities, in comparison to the unblocked" phenol subjected to condensation. An "unblocked phenol, is one having either two, or three ring positions available for reaction.

In the present invention, the amount of blocked phenol used, is less than equimolar quantities, the amounts varying from 0.1 to 0.9

mol for each full mol of the unblocked phenol employed.

The principal purpose of using less than equimolar quantities of blocked phenol in mixed phenol-formaldehyde condensations, is to create condensation products of planned molecular weight. The unblocked phenol used in the present invention is the p-tt-octylphenol first described by me in my Patent No. 2,008,032 (1935) and in Industrial and Engineering Chemistry, vol. 30, D. 1269 (1938). Condensing this phenol with formaldehyde and a blocked phenol, preferably p-tt-octyl-o-cresol, in acid medium, mixtures of polynuclear linear phenolic condensation products form, possessing a structure as indicated below;

condensation products formed mi ht b Pm- Fania 1 =9 9 9 CH CB;

gcumecngewnpt Kelsi)? Tamas; (Qua! cement Utilizing blocked phenols, asis the mamasjective and purpose of the instant invention,

the nin the above-formulas is approximately inversely proportional to the amount of blocked phenol used. The smaller the amount-of the "blocked phenoh'th'e higherthe average molecular weight of the final condensation products mixture. Since a number of physical properties and characteristics, such as melting point, fusion point, fluidity, viscosity, plasticity and oil solubility are to a large measure functions of the a molecular weight in these types of polymers, it is an achievement and discovery, not heretofore realized, that by judicious use of a blocked" phenol in these reactions, the creation of condensation products with predictable and predetermined properties is possible.

Besides the blocked phenol mentioned above, any other 2,4- or 26- dialkyl-phenol might be used. Such phenols are; the p-t-butyl-and p-tamyl-o-cresols; or the 2,4-di-t-butylthe 2,4- dit-amyland the 2,4- or the 2,6-dimethy1-phenols.

Example 1.C'ondensation in acid medium Nine hundredths of a mol of p-tt-octylphenol (18.5 grams) and one hundredth of a mol of p-ttoctyl-o-cresol (2.2 grams) are mixed with 8.5 grams of a 35.3% aqueous formaldehyde solution (0.1 mol). One cc. of concentrated hydrochloric acid is then added and the mixture well stirred. The reaction is allowed to continue for 48 hours at room temperature. After this time, the reaction mixture is heated or subjected to steam distillation to remove volatile material. The nonvolatile residue after washings with distilled water is separated and then allowed to dry in air.

The condensation product is a yellowish-brown solid which can be ground into a white powder. It has a lower fusion point than the condensation product obtained under the same reaction con- 3 ditions but with the p-tt-octylphenol alone. Also its solubility, in both boiling and cold benzene, is higher than that of the condensation product with the unblocked phenol alone.

Example 2.Condensation in alkaline medium Seven hundredths of a mol of p-tt-octylphenol (14.4 grams) and three hundredths of a mol of p-tt-octyl-o-cresol (6.6 grams) are first melted together and then well mixed. To this mixture is added 8.5 grams of a 35.3% aqueous formaldehyde solution (Olmol) and 015cc; of a?'30% aqueous sodium hydroxide'solution. The mixture is then well stirred or well shaken. After this, a

reflux condenser is attached to the reaction flask and the mixture heated on an oilbath at 125 C.

for two hours. After this time the condenser is changed and while heatingat the samev temperature for another 110111, the volatile materials pres- 4 Products according t claim 3 in which t '20 The condensation product mixture inthis case, is a semi-solid, with increased solubilities lnboth, I

l boiling and cold benzene. On the other hand, the

condensation product obtained when p-tt-octylent in the reaction mixture are thus distilled 01f.

2.- A process which consists essentially in form- 'ing a mixture of andcondensing p-tt-octylphnol with formaldehyde in the presenceof less than equimolar quantities of. 2-methyl-4-tt-octylphenol in the absence of unalkylated phenol, the

ratio of formaldehyde to alkylated phenols being equimolecular, and in the presence of a catalyst selected from the group of substances consisting of acids and alkalies.

3. Poly-nuclear linear phenolic condensation products having the followin structural formula:

OH on on R CHzO- CH CH2O- -CH7 R wherein R and R are alkyl'groups, said product being composed of blocked and unblocked phenols in the ratio 0.1 to 0.9 mol. of unblocked to 1 mol.

, -of blocked phenol, and n is approximately inversely proportional to the amount of blocked phenol.

least one of R is a methyl group.

.- v 5. Products according to claim 3 in which at 3 least one of R is a p-tt-octyl group,

6. Products according to claim 3 in which R is methyl and R is p-tt-octyl.

I JOSEPH B. NIEDERL. uREFEBENCES CI'I ED The followingreferences are of record in the file of this patent; I

-' UNITEDSTATESPATENTS Date Number Name 1,800,296 Honel Aug. 14, 1931 2,033,091 Bruson Mar. 3, 1936 2,049,447 Honel Aug. 4, 1936 Honel Dec. '6, 1938 OTHER REFERENCES I p 1 Granger Condensation of-phenols with'formal- Ind. Eng; Chem., vol. 24, Nov. 4, pp. 

